Bicyclic hindered amines

ABSTRACT

Compounds having the formula   WHEREIN R is alkyl, alkylene, phenyl, phenylene or alkyl substituted phenyl or phenylene, n is one or two and X is hydrogen, hydroxyl or oxygen, ARE GOOD LIGHT STABILIZERS. These compounds are prepared, for example, from 1,3,3-trimethyl-3-azabicyclo(2.2.2)octane-5-ol and stearic acid to give 5-stearoyloxy-1,3,3-trimethyl-2azabicyclo(2.2.2) octane which is converted by standard techniques to the corresponding 2-oxyl and 2-ol compounds.

United States Patent [191 Ramey et al.

[ Apr. 1,1975

[ BICYCLIC HINDERED AMINES [75] Inventors: Chester E. Ramey, SpringValley;

John J. Luzzi, Carmel. both of NY.

[73] Assignee: Ciba-Geigy Corporation, Ardsley.

[22] Filed: Dec. 28, 1973 [21] Appl. No.: 429,436

[52] US. Cl. 260/293.54, 260/45.8 N [51] Int. Cl C07d 39/00 [58] Fieldof Search 260/293.54

[56] References Cited FOREIGN PATENTS OR APPLICATIONS 1131.380 5/197]Great Britain zero/293.54

OTHER PUBLICATIONS Russat et al.. Tetrahedron 28(3), 74l50 (I972).

Primm'y E.\tuniner(i. Thomas Todd Allmm'y, Agc'nL 0r Firm-Nestor W.Shust; Charles W. Vanecek [57] ABSTRACT Compounds having the formula 8Claims, N0 Drawings 1 BICYCLIC HINDEIRED AMINES BACKGROUND OF THEINVENTION This invention relates to the stabilization of organicmaterial normally tending to deteriorate. In particular. the inventionrelates to the protection of synthetic polymers against the harmfuldegradative effects, such as discoloration and embrittlement caused byexposure to light, especially ultraviolet light.

It is known that actinic radiation, particularly in the near ultravioletregion. has a deleterious effect on both the appearance and propertiesof organic polymers. For example, normally colorless or light coloredpolyesters yellow on exposure to sunlight as do such cellulosics ascellulose acetate. Polystyrene discolors and cracks, with accompanyingloss of its desirable physical properties when exposed to actinic light.while vinyl resins, such as polyvinyl chloride and polyvinyl acetatespot and degrade. The rate of air oxidation of polyolefins such aspolyethylene and polypropylene is materially accelerated by ultravioletlight.

It has been proposed to stabilize polymeric materials againstultraviolet light deterioration by the use of various types ofultraviolet absorbers. Thus. U.S. Pat. No. 3.004.896 discloses for thispurpose (2(2-hydroxyphenyl)benzotriazole derivatives, while US. Pat. No.3.1891130 discloses certain metal salts of hydroxybenzoic acids whichare useful as actinic stabilizers in synthetic polymers.

DETAlLED DISCLOSURE The present invention is directed to a class ofultraviolet light stabilizers which consist of a compound of the formulawherein X is H, O. or OH,

11 is l or 2. and

a. when n is l. R is straightor branched-chain alkyl having I to carbonatoms. phenyl or phenyl substituted by one or more lower alkyl groups,and

b. when n is 2, R is straightor branched-chain alkylene having I to 20carbon atoms, phenylene or phenylene substituted by one or more loweralkyl groups.

Preferred compounds of formula I are those wherein The compounds asrepresented by formula I, can be used in combination with other lightstabilizers such as 2( Z-hydroxyphenyl )benzotriazoles, 2-hydroxybenzophenones. nickel complexes and benzoates. V

The compounds of this invention are stabilizers of organic materialnormally subject to thermal, oxidative or actinic light deterioration.Materials which are thus stabilized include synthetic organic polymericsubstances including homopolymers, copolymers, and mixtures thereof,such as vinyl resins formed from the polymerization of vinyl halides orfrom the copolymerization of vinyl halides with unsaturatedpolymerizable compounds, cg, vinyl esters, a,B-unsaturated acids,mB-unsaturated esters, a,,8-unsaturated ketones, afi-unsaturatedaldehydes and unsaturated hydrocarbons such as butadienes and styrene;poly-a-olefins such as high and low density polyethylene, crosslinkedpolyethylene. polypropylene, poly(4-methylpentene-l and the like,including copolymers of a-olefins; such as ethylene-propylenecopolymers, and the like; dienes such as polybutadiene, polyisoprene,and the like, including copolymers with other monomers; polyurethanessuch as are prepared from polyols and organic polyisocyanates, andpolyamides such as polyhexamethylene adipamide and polycaprolactam'.polyesters such as polyethylene terephthalates; polycarbonates such asthose prepared from bishphenol-A and phosgene', polyacetals such aspolyethylene terephthalate polyacetal; polystyrene. polyethyleneoxide;polyacrylics such as polyacrylonitrile; polyphenyleneoxides such asthose prepared from 2,6dimethylphenol and the like; and copolymers suchas those of polystyrene containing copolymers of butadiene and styreneand those formed by the copolymerization of acrylonitrile, butadieneand/or styrene.

Other materials which can be stabilized by the compounds of the presentinvention include lubricating oil of the aliphatic ester type, i.e., di(l,2-ethylene)- azelate, pentaerythritol tetracaproate, and the like;animal and vegetable derived oils, e.g., linseed oil, fat, tallow, lard,peanut oil, cod liver oil, castor oil, palm oil. corn oil, cottonseedoil, and the like; hydrocarbon materials such as gasoline, mineral oil,fuel oil, drying oil, cutting fluids, waxes, resins, and the like, saltsof fatty acids such as soaps and the like; and alkylene glycols, c.g.,B-methoxyethyleneglycol, methoxytriethyleneglycol, triethylene glycol,octaethyleneglycol, dibutyleneglycol, dipropyleneglycol and the like.

The compounds of this invention are particularly useful as UV lightstabilizers, especially for the protection of polyolefins, for instance,polyethylene, polypropylene, poly(butene-l poly(pentene-l poly (3-methylbutene-l poly(4-methylpentene-l various ethylene-propylenecopolymers and the like.

In general, the stabilizers of this invention are employed from about0.01 to about 5% by weight of the stabilized composition. although thiswill vary with the particular substrate and application. An advantageousrange is from about 0.05 to about 2% and especially 0.] to about 1%.

For addition to polymeric substrates, the stabilizers can be blendedbefore polymerization or after polymerization, during the usualprocessing operations, for example, by hot-milling, the composition thenbeing extruded, pressed, blow molded or the like into films, fibers,filaments, hollow spheres and the like. The heat stabilizing propertiesof these compounds may advantageously stabilize the polymer againstdegradation during such processing at the high temperature generallyencountered. The stabilizers can also be dissolved in suitable solventsand sprayed on the surface of films. fabrics, filaments or the like toprovide effective stabilization. Where the polymer is prepared from aliquid monomer as in the case of styrene, the stabilizer may bedispersed or dissolved in the monomer prior to polymerization or curing.

These compounds can also be used in combination with other additivessuch as antioxidants, sulfurcontaining esters such asdistearyl-B-thiodipropionate (DSTDP), diIauryl-B-thiodipropionate(DLTDP) in an amount of from 0.01 to 2% by weight of the organicmaterial, and the like, pourpoint depressants, corrosion and rustinhibitors, dispersing agents, demulsifiers, antifoaming agents, fillerssuch as glass or other fibers, carbon black, accelerators and the otherchemicals used in rubber compouding. plasticizers, color stabilizersdiand tri-alkyland -alkylphenylphosphites, heat stabilizers, ultravioletlight stabilizers, antiozonants, dyes, pigments, metal chelating agents,dyesites and the like. Often combinations such as these, particularlythe sulfur containing esters, the phosphites and/or the ultravioletlight stabilizers will produce superior results in certain applicationsto those expected by the properties of the individual components.

The following formula represents co-stabilizers which are in certaininstances very useful in combination with the stabilizers of thisinvention:

wherein R is an alkyl group having from 6 to 24 carbon atoms; and n isan integer from 1 to 6, Especially useful compounds of this type aredilauryl-B-thiodipropionate and distearyl-B-thiodipropionate. The abovecostabilizers are used in the amount of from 0.0l to 2% by weight of theorganic material, and preferably from 0.1 to 1%.

Although the compounds of this invention may to some degree also beeffective as thermal stabilizers, if

- the processing of the polymer is carried out at high temperatures itis advantageous to incorporate additional antioxidants.

In most applications, it is desirable to incorporate into the resincomposition, sufficient thermal antioxidants to protect the plasticagainst thermal and oxidative degradation. The amount of antioxidantrequired will be comparable to that of the actinic stabilizer. Namely,from about 0.005% to and preferably from 0.01% to 2% by weightRepresentative of such antioxidants are phosphite esters, such astriphenylphosphite and dibutylphosphite and alkyl arylphosphites such asdibutylphenylphosphite, and the like.

The best results have been obtained with the preferred class of thermalantioxidants, the hindered phenols. These compounds have been found toprovide the best thermal stabilization with the least discoloration inthe compositions of the invention. Among these phenolic antioxidants areincluded the following:

di-n-octadecyl(3-5-butyl-4-hydroxy-5-methylbenzyl )malonate2,6-di-t-butylphenol 2,2-methylene-bis(6-t-butyl-4-methylphenol)2,6-di-t-butylhydroquinone 1octadecyl-(3,S-di-t-butyl-4-hydroxybenzylthio) acetate l, l ,3-tris(3-t-butyl-6-methyl-4-hydroxyphenyl )butane l,4-bis(3,5-di-t-butyl-4-hydroxybenzyl )-2,3-5,6-tetramethylbenzene 2,4-bis-(3,5-di-t-butyl-4-hydroxyphenoxy )-6-( noctylthio l ,3,5-triazine2,4-bis-(4-hydroxy-3,S-di-t-butylphenoxy)-6-(noctylthioethylthio)-1,3,5-triazine2,4-bis-(n-octylthio)-6-(3,5-di-t-butyl-4-hydroxyanilino l ,3,S-triazine 2,4,6-tris-( 4-hydroxy-3,5-di-t-butylphenoxy l ,3 ,5

triazine n-octadecyl-B-(3,5-di-t-butyl-4-hydroxyphenyl)propionaten-octadecyl-3,5-di-t-butyl-4-hydroxybenzoate2-(n-octylthio)ethyl-3,5-di-t-butyl-4- hydroxybenzoate stearamidoN,N-bis-[ethylene hydroxyphenyl)propionate] l,2-propylene glycol bis-[3-( 3,5-di-t-butyl-4- hydroxyphenyl)propionate] pentaerythritoltetrakis-l 3-( 3,5-di-t-butyl-4-hydroxyphenyl )propionate]dioctadecyl-3,5-di-t-butyl-4-hydroxybenzylphosphonatedi-n-octadecyl-l-(3,5-di-t-butyl-4-hydroxyphenyl)- ethanephosphonate Theabove phenolic hydrocarbon stabilizers are known and many arecommercially available.

The above antioxidants have been listed only for the purpose ofillustration and it is important to note that any other antioxidant canbe employed with similar improved results. The above exemplifiedantioxidants and other related antioxidants which are incorporatedherein by reference, are disclosed in greater detail in the followingpatents:

Netherlands Patent Specification 67/] l 19, issued Feb. 19, 1968;Netherlands Patent Specificaton 68/03498 issued Sept. 18, 1968; US. Pat.Nos. 3,255,191; 3,330,859, 3,644,482, 3,281,505;

3,531,483, 3,285,855 3,364,250; 3,368,997; 3,357,944 and 3,758,549.

The compounds of formula I having the formula H OH, III

via a usual esterification procedure with an acid or di acid of theformula wherein R and n are as defined above, or with an acid anhydrideor mixed anhydride thereof. in the process of reacting an acid offormula IV with a compound of formula III the csterification catalyst ispreferably a neutral catalyst. for instance a tetraalkyl titanate.

Similarly. the novel esters of this invention may be prepared byconventional methods of transesterification. in the presence oftransesterification catalyst such as an alkali metal amide. for instancelithium amide.

The compounds of formula l wherein X is 0 may be prepared through thetreatment of a compound of formula ll by a conventional method ofoxidation, as for example by treatment with metachloroperbenzoic acid atroom temperature in methylene chloride solvent. Amont conventionaloxidizing reagents useful in the present invention are included otherpcracids such as perbenzoic acid. peracetic acid, hydrogenperoxide/EDTA/sodium tungstate. hydrogen peroxide/phosphotungstic acid.etc. The compounds of formula I wherein X is OH can be prepared. inturn. by a conventional catalytic hydrogenation of the compounds offormula I having X equal to O. as for example by treatment with H/Pd(c).

The compound of formula III may be prepared according to the proceduredescribed in British Patent l.23l.380 and in A. Rassat and P. Rey.Tetrahedron 28,741 (1972).

Synthesis of the intermediate piperitenone. of the formula boom. J. Org.Chem. 31. 2026 (I966). Piperitenone' has also been isolated as a naturalproduct from essential oils, as reported in Y. R. Naves.-Helv, Chem.Acta,

24. 722 (1951) and S. ShimizergN. -Ske'da,-and H.

Udea, Bull. Agr. Chem. Soc. Japan, 24. 324 (1960) and obtained by theoxidation of geranic acid, as reported in J. J. Berreboom, J. Am. Chem.Soc., 85. 3525 i963).

The acids. acid anhydrides. and esters which are reacted with thecompounds of formula Ill may all be prepared by methods well known inthe art. y

The following examples, presented for illustration and not limitation.will further serve to typify the nature of the present invention.

EXAMPLE I Piperitenone 4 A. To 1.0 1 of dry tetrahydrofuran; containedin a 5- liter 3-necked flask equipped with a stirrer. thermometer.condenser with drying tube, nitrogen inlet and dropping funnel was added40.0 g (0.73 moles) of pulverized KOH. To the resulting suspension wasadded. with stirring and cooling with an ice-salt bath, 686 g of mesityloxide at such a rate as to maintain the temperature of the reactionmixture below 30C. To the resulting solution was next added a solutionof /zg (2.5 moles) of methyl vinyl ketone in [96 g (total. 9 moles) ofmesityl oxide over a period of 0.8 hours while the temperature of thereaction mixture was maintained at 15 to 20C. The reaction mixture wasthen allowed to warm to room temperature and heated slowly to gentleboiling under reflux. After maintaining the boiling for 0.5 hours, thereaction mixture was cooled and 43 ml of glacial acetic acid'was addedwith stirring and cooling. The solvent and excess mesityl oxide wereremoved by distillation under a slight vacuum to a head temperature of78C and the residue was distilled under reduced pressure. The fractionboiling at 1 15 to l33/9 mm was retained. GLPC (20% silicon gum rubber.A inch 10 ft. column isothermal at C) of this fraction indicated thatthe anticipated products (piperitenone and isomers) were present.

To crude distillate (290 g) was added dropwise with stirring to asolution of 560 g of sodium sulfite in 2l of water. The solution washeated to 85C and 128 ml of glacial acetic acid was added dropwise overa 2 hour period to maintain the pH at 8-9. When the pH became steady forabout 0.5 hour., the mixture was cooled to room temperature andextracted with 3 X 250 ml ether. The aqueous layer was cooled in an icebath and the pH was adjusted to 13 by the addition of 70 ml of 50% NaOH.The basic aqueous solution was then extracted with 4 X 300 ml of ether.The ether extracts were combined dried over anhydrous sodium sulfate andevaporated to give 60.6 g of piperitenone. 96% pure by GLPC.

B. Among other methods of preparation, piperitenone is prepared in ananalogous manner to the procedure in (A) by substituting for the KOH.tetrahydrofuran used therein the following base, solvent combinations:

sodium t-pentoxide, toluene; barium oxide, benzene; potassiumt-butoxide, tetrahydrofuran; sodium hydride. tetrahydrofuran.

EXAMPLE 2 l ,3 ,3-Trimethyl-2-azabicyclo[2.2.2]octane 5-onehydrochloride A. In a 2-liter Morton flask equipped with a condenser.stirrer, thermometer and ice-salt cooling bath was placed [200 ml ofconcentrated ammonium hydroxide. To the flask was added dropwise withcooling and stirring 60.0 g (0.40 moles) of piperitenone over a 45minute period. The reaction mixture was allowed to stir and stand at -5Cfor 4 days. then allowed to warm to room temperature and stir overnight.The aqueous solution was then saturated with sodium chloride andextracted 3 X 300 ml with ether. The ether extracts were combined anddried over anhydrous sodium sulfate and evaporated under reducedpressure. The residue (55.5 g) was distilled at 30 to 35/0.003 mm giving45.5 g of material of about 85% purity by titration with standardperchloric acid in acetic acid with crystal violet as indicator. Aportion of the distillate (38.0 g) was dissolved in 700 ml ether and theether solution cooled to With stirring and cooling. anhydrous HCl wasbubbled into the ether until precipitation was complete. The ethersolution was heated to 50 for minutes. cooled. and filtered. Thecollected solid was washed well with ether and dried over P 0 in avacuum oven. giving 39.0 g of the desired aminoketone hydrochloride. Asmall sample of the hydrochloride was recrystallized from isopropanol.giving a white crystalline solid. m.p. 200204C.

B. Among other methods of preparation. the reaction described under (A)above is also performed by substituting anhydrous ammonia for theconcentrated ammonium hydroxide, by replacing the aqueous medium with anon-reactive solvent such as an ether. hydrocarbon or alcohol. and bypreferably conducting the reaction at greater than atmospheric pressure.

EXAMPLE 3 l.3.3-Trimethyl-3-azabicyclol 2.2. ]octane-5 ol A. In a l-l3-necked flask equipped with a stirrer. thermometer. condenser anddrying tube was placed 26.7 g (0.131 mole) ofl,3.3-trimethyl-2-azabicyclo[2.2.2]octane-S-one hydrochloride and 300 mlof absolute ethanol. The reaction mixture was cooled to 5C with anice-salt bath and 131 ml of l NKOH in methanol was added dropwise. Tothe solution was then added in small portions 2.6 g (0.069 moles) ofNaBH over a 0.5 hour period. The solution was allowed to stir at 05C for1.5 hours and then allowed to warm to room temperature and stirovernight. The reaction mixture was then made acidic by the addition of78 ml of concentrated HCl, filtered and the filtrate was evaporated todryness under reduced pressure. The residue was brought to pH 12 with 2NKOH and extracted 3 X 100 ml with CH Cl The organic extracts werecombined, dried over anhydrous potassium carbonate and evaporated.yielding 9.5 g of colorless crystals, m.p. 120 to l23C*. afterrecrystallization from hexane. lit.. m.p. l23C (A. -Rassat & P. Rey.Tetrahedron 28 741 (I972) B. Among other methods of preparation. thereaction described under (A) above is also performed by replacing thereducing medium by:

lithium aluminum hydride/ether or tetrahydrofuran; lithium/liquid NH/ethanol; lithium/liquid NH sodium/ethanol.

The latter two reagents give a mixture of two isomeric alcohols.

EXAMPLE 4 5-stearoyloxyl-l .3.3-trimethyl-2- azabicyclol 2.2.2]octane A.In a 300 ml 3-necked flask equipped with a stirrer. thermometer.condenser with water separator, drying tube and N inlet was placed 150ml of dry xylene, 5.1 g (0.03 moles) ofl,3,3-trimethyl-2-azabicyclo[2.2.- 2]octane-5-ol, 8.529 g (0.03 moles)of stearic acid and 0.89 ml (0.003 moles) of tetraisopropyl titanate.The reaction mixture was boiled under reflux with stirring for 2 days.At the end of this time, the reaction mixture was cooled. diluted withan equal volume of ether, washed 2 X ml with water and dried overanhydrous sodium sulfate. The ether-xylene solution was evaporated underreduced pressure and the residue recrystallized from acetoneacetonitrileyielding 3.5 g of the desired material as white crystals, m.p. 41 to45C.

B. By essentially following the above procedure (A) and substituting forthe stearic acid an equivalent amount of a. acetic acid b. benzoic acidc. decanoic acid (1. butyric acid 6. isovaleric acid f.2,4.6-trimethylbenzoic acid g. 4-methylbenzoic acid there isrespectively obtained the following compounds:

a. 5-acetoxy-l ,3.3-trimethyl-2- azabicyclol2.2.2]octane S-benzoyloxyl.3.3-trimethyl-2- azabicyclol 2.2.2loctane c. S-decanoyloxy-l.3.3-trimethyl-2- azabicyclo[2.2.2]octane S-butyroyloxy-l.3.3-trimethyl-2- azabicyclo[2.2.2]octane e. 5-isovaleroyloxy-l,3,3-trimethyl-2- azabicyclo[2.2.2]octane f. 5-(2,4,6-trimethylbenzoyloxy )-l ,3.3-trimethyl-2- azabicyclo[2.2.2]octaneg. 5-(4-methylbenzoyloxy )-l ,3,3-trimethyl-2- azabicycloI 2.2.2]octane.

EXAMPLE 5 Bis( 1,3 ,3-trimethyl-2-azabicyclol 2.2.2 ]octane-S-ol)sebacate A. In a 300 ml 3-necked flask equipped with stirrer,thermometer. condenser with water separator, drying tube and N inlet wasplaced 5.1 g (0.03 moles) of 1,3,-3-trimethyl-2-azabicyclo[2.2.2]octane-5-ol. 200 ml of dry xylene. 3.45 g(0.0l7 moles) of sebacic acid and 0.85 g (0.89 ml, 0.003 moles) oftetraisopropyl titanate. The reaction mixture was boiled under refluxwith stirring for 3 days. At the end of this time the reaction mixturewas cooled to room temperature and decanted from the residual solidswhich remained in the reaction flask. The xylene solution was washedwith 100 ml of water. thenwith 100 ml of 2N NaOH. during which time anemulsion'formed. The emulsion was treated with ether; and dried overanhydrous Na SO The etherxylene solution was evaporated under reducedpressure leaving a viscous residue which by elemental analysis'andspectra proved to be the desired material.

B. By essentially following the above procedure (A) and substituting forthe sebacic acid an equivalent amount of a. succinic acid b. phthalicacid c. dodecanedicarboxylic acid d. isophthalic acid e. terephthalicacid f. tetramethylsuecinic acid g. 4.6-dimethylisophthalic acid h.S-methylisophthalic acid there is respectively obtained the followingcompounds:

a. bis( l.3.3-trimethyl-2-azabicyclol2.2.2]octane-5- ol)succinate b.bis( l,3.3-trimethyl-2-azabicyclol 2.2.2]octane-5 ol)phthalate c.bis(l.3.3-trimethyl-2-azabicyclol2.2.2]octane-5- ol)dodecanedicarboxylate d. bis(l.3.3-triniethyl-2azabicyclo[2.2.2]octane-5- ol)isophthalate e. bis(l.3.3-trimethyl-2-azabicyclol2. ol)terephthalate f. bis(l.3,3-trimethyl-2-azabicyclo[2.2.2]octane5- ol)tetramethylsuccinate g.bis( l.3.3-trimethyl-2-azabicycloI 2.2.2]octane-5-ol)4.o-dimethylisophthalate h. bis( 1.3 .3-trimethyl-2-azabicyclo[ 2.2.2]octane-5- ol)S-methylisophthalate. I

EXAMPLE 6 S-Acetoxyl ,3.3-trimethyl-2-azabicyclol 2.2.2 ]octane 2.2]octane-5- To a solution of 1.8 g (0.016 moles) of 1.3.3-

trimethyl-2-azabicyclol2.2.2]octane-5-ol in 30 ml of glacial acetic acidin a 100 ml flask equipped with a magnetic stirrer. thermometer,condenser, and drying tube was added 1.0 ml (0.106 moles) of aceticanhydride. The solution was boiled under reflux for 20 hours. Thereaction mixture was then cooled and evaporated under reduced pressure.The residue was taken up in hexane. and allowed to stand at roomtemperature overnight. The solution was then filtered and the filtrateevaporated under reduced pressure and dried under vacuum at 35C,yielding 1.23 g of the desired material as a colorless oil.

EXAMPLE 7 S-Stearoyloxy-l .3.3-trimethyl-2-oxyl-2- azabicyclo[ 2.2.2]octane A. To a solution of 2.5 g (0.0057 moles) of 5- stearoyloxyl.3,3-trimethyl-2-azabicyclo[ 2.2.2 ]octane in 50 ml of methylenechloride in a 200 ml 3necked flask equipped with a stirrer. thermometer,nitrogen inlet and dropping funnel was added dropwise with stirring asolution of 2.3 g (0.0114 moles) of 85% metachloroperbenzoic acid in 70ml of methylene chloride. The reaction was allowed to stir at roomtemperature overnight and a bright yellow color developed. The reactionmixture was then washed with 100 ml 1N NaOH, l ml water, and evaporatedunder reduced pressure. The residue was recrystallized several timesfrom petroleum ether giving l.3 g of the desired materials as orangecrystals. m.p. 5356C.

B. By essentially following the above procedure (A) and substituting forthe -stearoyloxyl,3,3-trimethyl- 2-azabicyclol2.2.2]octane andequivalent amount of a. 5-acetoxy-l ,3,3-trimethyl-2-azabicyclol2.2.2]octane 5-benzoyloxy- 1 ,3,3-trimethyl-2-azabicyclo[2.2.2]octane c.bis(1.3,3-trimethyl-2-azabicyclo[2.2.2]octane-5- ol)sebacate d.bis(l,3,3-trimethyl-2-azabicyclo[2.2.2]octane-5- ol)terephthalate thereis respectively obtained the following compounds:

a. S-acetoxy-l ,3,3-trimethyl-2-oxyl-2- azabicyclol2.2.2]octane b.S-benzoyloxy-l.3,3-trimethyl-2-oxyl-2 -azabicyclo[2.2.2]octane c.bis(l,3,3-trimethyl-2-oxyl-2-azabicyclol2.2.2]octane5-ol )sebacate d.bis( l,3,3-trimethyl-2-oxyl-2-azabicyclo[2.2.2]octane-501)terephthalate.

EXAMPLE 8 S-Stearoyloxyl ,3,3-trimethyl-2-ol-2- azabicyclol 2.2.2]octaneA. To a solution of S-stearoyloxy-l.3,3-trimethyl-2-oxyl-2-azabicyclo[2.2.2]octane in warm glacial acetic acid is added 5%Pd on charcoal. The acetic acid solution is placed in a ParrHydrogenation apparatus and hydrogenated at 45 psi H for 0.5 hr. At theend of this time. the reaction mixture is poured into water andextracted with 3 X 200 ml ether. The ether extracts are combined, driedover anhydrous Na SO and evaporated yielding the desired material.

B. By following the above procedure. and substituting forS-stearoyloxy-l.3.3-trimethyl-2-oxyl-2- azabicycl0[2.2.2]octane thefollowing compounds:

a. S-benzoyloxyl .3,3-trimethyl-2-oxyl-2- azabicyclo[2.2.2]octane b.bis( l,3.3-trimethyl-2-oxyl-2-azabicyclol2.2.2]octane5-ol sebacate 0.bis( l,3.3-trimethyl-2-oxyl-2-azabicyclo[2.2.2]octane-S-ol)terephthalate there is respectivelyobtained the following compounds:

a. S-benzoyloxy-l,3,3-trimethyl-2-ol-2- azabicyclo[2.2.2]octane b. bis(1 ,3,3-trimethyl-Z-ol-Z-azabicyclol 2.2.2]octane-5-ol)sebacate c.bis(1,3,3-trimethyl-2-ol-2- azabicyclol 2.2.2 ]octane-5-ol)terephthalate.

EXAMPLE 9 Artificial Light Exposure Test Deterioration of most polymerscaused by ultraviolet light is so slow at ambient temperatures, even inthe absence of stabilizers, that testing of the effects of stabilizersgenerally must be conducted either at higher temperatures or in anaccelerated artificial light exposure device in order to yield resultsin a convenient period of time. The tests conducted in polymers using anartificial light exposure device is described below:

a. Sample Preparation 5 mil Film Unstabilized polypropylene powder(Hercules Profax 6501) is thoroughly blended with the indicated amountsof additives. The blended material is then milled on a two roll mill for5 minutes at l82C. The milled sheet is then compression molded at 220Cinto mil thick film under a pressure of 175 psi and water cooled in thepress.

b. Testing Method This test is conducted in a FS/BL unit, basically ofthe American Cyanamid design. which consists of 40 tubes of alternatingfluorescent sunlamps and black lights of each). The 5 mil sample filmwhich are mounted on 3 X 2 inches IR card holders with A X 1 inchwindows and are placed on a rotating drum 2 inches from the bulbs in theFS/BL unit. The time in hours is noted for the development of 0.5carbonyl absorbance units as determined on an Infrared Spectophotometer.The development of carbonyl functional groups in the polymer isproportional to the amount of degradation caused by the ultravioletlight exposure.

The test results reported below were obtained according to theprocedures described above. The amounts of the additives are expressedin weight percent based on the weight of the polymer.

TABLE I EXAMPLE 10 High impact polystyrene resin containing elastomer(i.e. butadiene-styrene) is stabilized against loss of elongationproperties due to exposure to ultraviolet light by incorporation of 0.3%by weight of 5- stearoyloxy-l .3,3-trimethyl-2-oxyl-2-azabicyclol2.2.2]octane.

The unstabilized resin is dissolved in chloroform and the stabilizerthen added. after which the mixture is cast on a glass plate and thesolvent evaporated to yield a uniform film which, upon drying, isremoved and cut up. and then pressed for 7 minutes at a temperature of[63C and a pressure of 2,000 pounds per square inch into a sheet ofuniform thickness mil). The sheets are then cut into stripsapproximately 4 X 0.5 inches. A portion of these strips is then measuredfor percent of elongation in the lnstron Tensile Testing Apparatus(lnstron Engineering Corporation, Quincy, Massachusetts). The remainingportions of the strips are Light Stabilization Data in PolypropyleneTime in Hours to 0.5 Carbonyl Additive Absorhance Units Formulation A*5-acetoxyl .3.3-trimethyl-2-azabicyclo Formulation 8* 3.5-di-t-hutyl--1hydroxyhenzylphosphonate Proportionatcly good stabilization is obtainedwhen in the compositions of Table l the compounds of this invention arepresent in the concentrations of 0.17: and 1%.

Other hindered phenolic antioxidants may be used in place ofdi-octadecyl(3,5-di-t-butyl-4-hydroxybenzyl)- phosphonate in the abovementioned compositions for example, di-n-octadecyla-(3-t-butyl-4-hydroxy-4- methylbenzyl )malonate,2,4-bis(n-octylthio)-6-( 3,4-dit-butyl-4-hydroxyaniline l .3.5-triazine.octadecyl 3-(3', 5'-di-t-butyl-4'-hydroxyphenyl)propionate.pentaerythritol-tetrakisl 3-(3,5-di-t-butyl-4-hydroxyphenyl)]propi0nate,tris-(3.5-di-t-butyl-4-hydroxybenzyl)isocyanurate,2.6-di-tert-butyl-4-methylphenol, N,- N,N-tris-( 3.5-di-tert-butyl-4-hydroxybenzyl )isocyanurate, and2,4,6-tris(3.S-di-tert-butyl-4-hydroxybenzyl)- 1,3.5-trimethylbenzyl.

The compositions of Table I are also stabilized with 2(2-hydroxy-3,5'-di-t-butylphenyl)-5- chlorobenzotriazole is replaced with thefollowing UV absorbers:

a. 2-hydroxy-4-methoxy-5sulfobenzophenone trihydrate b.2-hydroxy-4-n-octoxybenzophenone c.[2,2-thiobis(4-t-octylphenolate)l-n-butylamine nickel ll d.p-octylphenyl salicylate e. 2,2'-dihydroxy-4 4'-dimethoxybenzophenone f.2(2-hydroxy-5-methylphenyl )-benzotriazole.

placed in an FS/BL chamber according to Example 7(B) except that thesamples are mounted and white cardboard stock and the time to 50%reduction in elongation is measured. The stabilized polystyrene resinretains its elongation property longer than the unstabilized resin.

EXAMPLE ll Unstabilized linear polyethylene is solvent blended inmethylene chloride with 0.5% by weight of the substrate of S-acetoxy-l,3 .3-trimethyl-2- azabicyclol2.2.2]octane and then vacuum dried. Theresin is then extrusion compounded on a 1 inch 24/l=L/D extruder. melttemperature 450F (232C) and pressed for 7 minutes at a temperature of163C and a pressure of 2000 psi into a sheet of uniform thickness ofmil. The sheets are then cut into plaques of 2 inch X 2 inch. Theplaques are then exposed in a FS/BL exposure device and colormeasurements made periodically using a Hunter Color Difference MeterModel D25. Polyethylene stabilized with the above compound is found tobe much more stable than the unstabilized polyethylene or thepolyethylene stabilized only with an antioxidant.

EXAMPLE 12 A quantity of SBR'emulsion containing 100 g of rubber (500 mlof SBR obtained from Texas U .-S.. Synpol 1500) previously stored under;nitrogen. is placed in a beaker and stirred vigorously. The pH oftheemulsion is adjusted to 10.5 with a 0.5N NaOH solution. y

To the emulsion is added 50 ml of NaCl solution. A 6% NaCl solutionadjusted with hydrochloric acid to a pH 1.5 is added in a thin streamwith vigorous stirring. When pH 6.5 is reached. the rubber begins tocoagulate and the addition is slowed down in order to maintain uniformagitation. The addition of the acidic 6% NaCl solution is terminatedwhen a pH 3.5 is reached. The coagulated crumb-rubber slurry at pH 3.5is stirred for one-half hour.

The coagulated rubber is isolated by filtration through cheese cloth.and rinsed with distilled water. After three subsequent washings withfresh distilled water. the coagulated rubber is dried. first at 25 mm Hgand finally to constant weight under high vacuum 1 mm) at 4045C.

The dried rubber (25 g) is heated under nitrogen at 125C in a Brabendermixer and to this is added with mixing 0.25 g (0.5%) of bis(1.3.3-trimethyl-2- azabicyclol 2.2.2loctane-5-o1)sebacate. is mixed for5 minutes after which it is cooled and compression molded at 125C into 5X 0.025 inches plaques.

The plaques are exposed to a xenon arc weatherome ter and the colormeasurement (L-b) is made after 45. 125 and 290 hours. The samplesstabilized with the above compound are found to be much more lightstable than the unstabilized samples.

EXAMPLE 13 To 50 g of polyacetal resin containing 0.1% of an acidscavenger. dicyandiamide. is added 0.2% by weight of 5-benzoyloxy-l .3.3-trimethyl2- azabicyclol2.2.21octane and milled for 7 minutes at 200Cin a Brabender Plasti-recorder. The milled formulation is subsequentlypressed into a 40 mil sheet at 215C at 350 psi for 90 seconds thencooled quickly in a cold press at 350 psi. The stabilized sheets arethen remolded for 2 minutes at contact pressure and for 3 minutes at 300psi at 215C to give plaques 1 /2 inch X 2 /4 inch X 125 mil. Thereafter.the testing procedure of Example 9 is followed to determine the lightstability of the samples. The stabilized samples are found to be muchmore stable than the unstabilized samples.

EXAMPLE l4 Unstabilized thoroughly dried polyethylene terephthalatechips are dry blended with 1.0% of 5- stearoyloxy- 1.3.3-trimethyl-2-azabicyclol 2.2.2]octane: 60/10 denier multifilament is melt spun at amelt temperature of 290C. The oriented fiber is wound on white cards andexposed in a Xenon Arc Fadeometer. Color measurements are madeperiodically with a Hunter Color Difference Meter Model D25. Thestabilized samples are found to be much more light stable than theunstabilized samples.

EXAMPLE 15 a. A composition comprising acrylonitrile-butadienestyreneterpolymer and 1% by weight of the bis( 1,3,3-trimethyl-2azabicyclo[2.2.21octane-5- 1 4. ol)terephthalate resistsembrittlement due to exposure to ultraviolet light longer than one whichdoes not contain the stabilizer.

b. A composition comprising polyurethane prepared from toluenediisocyanate and -alkylene polyols and 1.0% by weight ofS-acetoxy-l,3J-trimethyl-Z-oxyl-Z- azabicyclo[2.2.2loctane is morestable to sunlight. fluorescent sunlamps, black lights and fluorescentlights than the unformulated polyurethane.

c. A composition comprising a polycarbonate prepared from bisphenol-Aand phosgene and 1% by weight of 5-stearoyloxy- 1 ,3.3-trimethyl-2-ol-2- azabicyclol2.2.21octane resists discoloration dueto exposure to ultraviolet light longer than one which does not containthe stabilizer.

d. A composition comprising polymethylmethacrylate and 0.25% by weightof bis(l,3,3-trimethyl-2- azabicycloI2.2.2]octane-5-ol)succinate resistsdiscoloration due to exposure to ultraviolet light longer than one whichdoes not contain the stabilizer.

EXAMPLE 16 a. A stabilized polyamide (nylon 6,6) is prepared byincorporating therein 0.1% of bis( 1.3.3-trimethyl-2-azabicyclol2.2.2loctane-5-ol)terephthalate. The light stability of thestabilized composition is superior to that of an unstabilized polyamide.

b. A stabilized polyphenylene oxide polymer (prepared by polymerizing2,6-dimethylphenol is prepared by incorporating therein 05% by weight of5- stearoyloxy-l .3.3-trimethyl-2- azabicyclo[2.2.2loctane. Thestabilized compositions resist embrittlement due to exposure toultraviolet light longer than one which does not contain the stabilizer.

c. A stabilized crystalline polystyrene is prepared by incorporatingtherein 0.1% by weight of bis( 1.3.3- trimethyl-2-azabicyclo[2.2.2]octane-5-ol )sebacate. The stabilized composition resistsembrittlement due to exposure to ultraviolet light longer than one whichdoes not contain the stabilizer.

Antioxidants may also be incorporated into each of the above mentionedcompositions, for example.di-noctadecyla,a'-bis(3-butyl-4-hydroxy-S-methylbenzyl) malonate2.4-bis(4-hydroxy-3.5-di-t-butylphenoxy)-6-(n-octylthioethylthio)-1,3,5-triazine,2,4-bis(3,5-di-tbutyl-hydroxyphenoxy)-6-(n-octylthio)-1.3,5-triazinedi-n-octadecyl 3(3,5-dit-butyl-4 hydroxyphenyl)propionate, respectively.

What is claimed is:

l. A compound of the formula 9 l bC-- n LII atoms.

5. A compound according to claim 2 which is 5- acetoxyl.3,3-trimethyl-2-azabicyclo[ 2.2.2 loctane.

6. A compound according to claim 2 which is 5- stearoyloxy-l.3.3-trimethyl-2- azabicyclol2.2.2loctane.

7. A compound according to claim 2 which is bis( 1,3-.3-trimethyl-2-azabicyclo[ 2.2.2 ]octane-5-ol )sebacate.

8. A compound according to claim 2 which is 5- stearoyloXy-l,3.3-trimethyl-2-oxyl-2- azabicyclol 2.2.21octane.

1. A COMPOUND OF THE FORMULA
 2. A compound according to claim 1 whereinX is H or O.
 3. A compound according to claim 2, wherein a. when n is 1,R is phenyl or n-alkyl having 1 to 20 carbon atoms, and b. when n is 2,R is phenylene or n-alkylene having 1 to 12 carbon atoms.
 4. A compoundaccording to claim 2, wherein a. when n is 1, R is n-alkyl having 1 to20 carbon atoms, and b. when n is 2, R is n-alkylene having 1 to 12carbon atoms.
 5. A compound according to claim 2 which is5-acetoxy-1,3,3-trimethyl-2-azabicyclo(2.2.2)octane.
 6. A compoundaccording to claim 2 which is5-stearoyloxy-1,3,3-trimethyl-2-azabicyclo(2.2.2)octane.
 7. A compoundaccording to claim 2 which isbis(1,3,3-trimethyl-2-azabicyclo(2.2.2)octane-5-ol)sebacate.
 8. Acompound according to claim 2 which is5-stearoyloxy-1,3,3-trimethyl-2-oxyl-2-azabicyclo( 2.2.2)octane.